Fabrication of Large-Area Molybdenum Disulfide Device Arrays Using Graphene/Ti Contacts.

Two-dimensional (2D) molybdenum disulfide (MoS2) is the most mature material in 2D material fields owing to its relatively high mobility and scalability. Such noticeable properties enable it to realize practical electronic and optoelectronic applications. However, contact engineering for large-area MoS2 films has not yet been established, although contact property is directly associated to the device performance. Herein, we introduce graphene-interlayered Ti contacts (graphene/Ti) into large-area MoS2 device arrays using a wet-transfer method. We achieve MoS2 devices with superior electrical and photoelectrical properties using graphene/Ti contacts, with a field-effect mobility of 18.3 cm2/V∙s, on/off current ratio of 3 × 107, responsivity of 850 A/W, and detectivity of 2 × 1012 Jones. This outstanding performance is attributable to a reduction in the Schottky barrier height of the resultant devices, which arises from the decreased work function of graphene induced by the charge transfer from Ti. Our research offers a direction toward large-scale electronic and optoelectronic applications based on 2D materials.

Tunable Ion Sieving of Graphene Membranes through the Control of Nitrogen-Bonding Configuration.

Graphene-oxide (GO) membranes with notable ionic-sieving properties have attracted significant attention for many applications. However, the swelling and unstable nanostructure of GO laminates in water results in enlarged interlayer spacing and a low permeation cut-off, limiting their applicability for water purification and desalination. Herein, we propose novel nitrogen-doped graphene (NG) membranes for use in tunable ion sieving that are made via facile fabrication by a time-dependent N-doping technique. Doping reaction time associated variation in atomic content and bonding configurations strongly contributed to the nanostructure of NG laminates by yielding narrower interlayer spacing and a more-polarized surface than GO. These nanostructural features subsequently allowed ion transport through the combined mechanisms of size exclusion and electrostatic interaction. The stacked NG membranes provided size-dependent permeability for hydrated ions and improved ion selectivity by 1-3 orders of magnitude in comparison to that of a GO membrane. For ions small enough to move through the interlayer spacing, the ion permeation is determined by electrostatic properties of NG membranes with the type of N configuration, especially polarized pyridinic N. Due to these properties, the NG membrane functioned as an unconventionally selective graphene-based membrane with better ion sieving for water purification.

Control over Electron-Phonon Interaction by Dirac Plasmon Engineering in the Bi2Se3 Topological Insulator.

Understanding the mutual interaction between electronic excitations and lattice vibrations is key for understanding electronic transport and optoelectronic phenomena. Dynamic manipulation of such interaction is elusive because it requires varying the material composition on the atomic level. In turn, recent studies on topological insulators (TIs) have revealed the coexistence of a strong phonon resonance and topologically protected Dirac plasmon, both in the terahertz (THz) frequency range. Here, using these intrinsic characteristics of TIs, we demonstrate a new methodology for controlling electron-phonon interaction by lithographically engineered Dirac surface plasmons in the Bi2Se3 TI. Through a series of time-domain and time-resolved ultrafast THz measurements, we show that, when the Dirac plasmon energy is less than the TI phonon energy, the electron-phonon coupling is trivial, exhibiting phonon broadening associated with Landau damping. In contrast, when the Dirac plasmon energy exceeds that of the phonon resonance, we observe suppressed electron-phonon interaction leading to unexpected phonon stiffening. Time-dependent analysis of the Dirac plasmon behavior, phonon broadening, and phonon stiffening reveals a transition between the distinct dynamics corresponding to the two regimes as the Dirac plasmon resonance moves across the TI phonon resonance, which demonstrates the capability of Dirac plasmon control. Our results suggest that the engineering of Dirac plasmons provides a new alternative for controlling the dynamic interaction between Dirac carriers and phonons.

Chemically Functionalized, Well-Dispersed Carbon Nanotubes in Lithium-Doped Zinc Oxide for Low-Cost, High-Performance Thin-Film Transistors.

Surface-functionalized carbon nanotubes (CNTs) are introduced into lithium-doped ZnO thin-film transistors (TFTs) as an alternative to the conventional incorporation of an expensive element, indium. The crucial role of surface functionalization of CNTs is clarified with the demonstration of indium-free ZnO-based TFTs with a field-effect mobility of 28.6 cm(2) V(-1) s(-1) and an on/off current ratio of 9 × 10(6) for low-cost, high-performance electronics.

Graphene interlayer for current spreading enhancement by engineering of barrier height in GaN-based light-emitting diodes.

Pristine graphene and a graphene interlayer inserted between indium tin oxide (ITO) and p-GaN have been analyzed and compared with ITO, which is a typical current spreading layer in lateral GaN LEDs. Beyond a certain current injection, the pristine graphene current spreading layer (CSL) malfunctioned due to Joule heat that originated from the high sheet resistance and low work function of the CSL. However, by combining the graphene and the ITO to improve the sheet resistance, it was found to be possible to solve the malfunctioning phenomenon. Moreover, the light output power of an LED with a graphene interlayer was stronger than that of an LED using ITO or graphene CSL. We were able to identify that the improvement originated from the enhanced current spreading by inspecting the contact and conducting the simulation.

Effects of multi-layer graphene capping on Cu interconnects.

The benefits of multi-layer graphene (MLG) capping on Cu interconnects have been experimentally demonstrated. The resistance of MLG capped Cu wires improved by 2-7% compared to Cu wires. The breakdown current density increased by 18%, suggesting that the MLG can act as an excellent capping material for Cu interconnects, improving the reliability characteristics. With a proper process optimization, MLG capped Cu interconnects could become a promising technology for high density back end-of-line interconnects.

M13 phage-functionalized single-walled carbon nanotubes as nanoprobes for second near-infrared window fluorescence imaging of targeted tumors.

Second near-infrared (NIR) window light (950-1400 nm) is attractive for in vivo fluorescence imaging due to its deep penetration depth in tissues and low tissue autofluorescence. Here we show genetically engineered multifunctional M13 phage can assemble fluorescent single-walled carbon nanotubes (SWNTs) and ligands for targeted fluorescence imaging of tumors. M13-SWNT probe is detectable in deep tissues even at a low dosage of 2 µg/mL and up to 2.5 cm in tissue-like phantoms. Moreover, targeted probes show specific and up to 4-fold improved uptake in prostate specific membrane antigen positive prostate tumors compared to control nontargeted probes. This M13 phage-based second NIR window fluorescence imaging probe has great potential for specific detection and therapy monitoring of hard-to-detect areas.

Anomalous thickness-dependence of photocurrent explained for state-of-the-art planar nano-heterojunction organic solar cells.

Due to their simple geometry and design, planar heterojunction (PHJ) solar cells have advantages both as potential photovoltaics with more efficient charge extraction than their bulk heterojunction (BHJ) counterparts, and as idealized interfaces to study basic device operation. The main reason for creating BHJs was the limited exciton diffusion length in the active materials of the PHJ: if an exciton is generated at a distance greater than its diffusion length from the hetero-interface of the PHJ, it would be very unlikely to be able to contribute to the photocurrent. Based on this argument one expects a maximum in the photocurrent of PHJs for a thickness of the active layer equal to the exciton diffusion length (~10 nm). However, in two recently developed PHJs that have appeared in the literature, a maximum photocurrent is observed for 60-65 nm of poly(3-hexylthiophene) (P3HT). In this work, we explore this anomaly by combining both an optical T-matrix and a kinetic Monte Carlo simulation that tracks the exciton behavior in the PHJs. The two systems considered are a P3HT/single walled carbon nanotube (SWNT) device, and a P3HT/phenyl-C61-butyric acid methyl ester (PCBM) device. The model demonstrates how a bulk exciton sink can explain the shifted maximum in the P3HT/SWNT case, whereas in the P3HT/PCBM case the maximum is mainly determined by PCBM molecules interdiffusing in the P3HT upon annealing. Based upon the results of this model it will be possible to more intelligently design nanostructured photovoltaics and optimize them toward higher efficiencies.

Dynamics of simultaneous, single ion transport through two single-walled carbon nanotubes: observation of a three-state system.

The ability to actively manipulate and transport single molecules in solution has the potential to revolutionize chemical synthesis and catalysis. In previous work, we developed a nanopore platform using the interior of a single-walled carbon nanotube (diameter = 1.5 nm) for the Coulter detection of single cations of Li(+), K(+), and Na(+). We demonstrate that as a result of their fabrication, such systems have electrostatic barriers present at their ends that are generally asymmetric, allowing for the trapping of ions. We show that above this threshold bias, traversing the nanopore end is not rate-limiting and that the pore-blocking behavior of two parallel nanotubes follows an idealized Markov process with the electrical potential. Such nanopores may allow for high-throughput linear processing of molecules as new catalysts and separation devices.

Exciton antennas and concentrators from core-shell and corrugated carbon nanotube filaments of homogeneous composition.

There has been renewed interest in solar concentrators and optical antennas for improvements in photovoltaic energy harvesting and new optoelectronic devices. In this work, we dielectrophoretically assemble single-walled carbon nanotubes (SWNTs) of homogeneous composition into aligned filaments that can exchange excitation energy, concentrating it to the centre of core-shell structures with radial gradients in the optical bandgap. We find an unusually sharp, reversible decay in photoemission that occurs as such filaments are cycled from ambient temperature to only 357 K, attributed to the strongly temperature-dependent second-order Auger process. Core-shell structures consisting of annular shells of mostly (6,5) SWNTs (E(g)=1.21 eV) and cores with bandgaps smaller than those of the shell (E(g)=1.17 eV (7,5)-0.98 eV (8,7)) demonstrate the concentration concept: broadband absorption in the ultraviolet-near-infrared wavelength regime provides quasi-singular photoemission at the (8,7) SWNTs. This approach demonstrates the potential of specifically designed collections of nanotubes to manipulate and concentrate excitons in unique ways.

Dynamic and reversible self-assembly of photoelectrochemical complexes based on lipid bilayer disks, photosynthetic reaction centers, and single-walled carbon nanotubes.

An aqueous solution containing photosynthetic reaction centers (RCs), membrane scaffold proteins (MSPs), phospholipids, and single-walled carbon nanotubes (SWCNTs) solubilized with the surfactant sodium cholate (SC) reversibly self-assembles into a highly ordered structure upon dialysis of the latter. The resulting structure is photoelectrochemically active and consists of 4-nm-thick lipid bilayer disks (nanodisks, NDs) arranged parallel to the surface of the SWCNT with the RC housed within the bilayer such that its hole injecting site faces the nanotube surface. The structure can be assembled and disassembled autonomously with the addition or removal of surfactant. We model the kinetic and thermodynamic forces that drive the dynamics of this reversible self-assembly process. The assembly is monitored using spectrofluorimetry during dialysis and subsequent surfactant addition and used to fit a kinetic model to determine the forward and reverse rate constants of ND and ND-SWCNT formation. The calculated ND and ND-SWCNT forward rate constants are 79 mM(-1) s(-1) and 5.4 × 10(2) mM(-1) s(-1), respectively, and the reverse rate constants are negligible over the dialysis time scale. We find that the reaction is not diffusion-controlled since the ND-SWCNT reaction, which consists of entities with smaller diffusion coefficients, has a larger reaction rate constant. Using these rate parameters, we were able to develop a kinetic phase diagram for the formation of ND-SWCNT complexes, which indicates an optimal dialysis rate of approximately 8 × 10(-4) s(-1). We also fit the model to cyclic ND-SWCNT assembly and disassembly experiments and hence mimic the thermodynamic forces used in regeneration processes detailed previously. Such forces may form the basis of both synthetic and natural photoelectrochemical complexes capable of dynamic component replacement and repair.

Substitutional Fluorine Doping of Large-Area Molybdenum Disulfide Monolayer Films for Flexible Inverter Device Arrays.

Reliable and controllable doping of transition metal dichalcogenides (TMDCs) is a mandatory requirement for practical large-scale electronic applications. However, most of the literature on the doping methodologies of TMDCs has focused on n-type doping and multilayer TMDC rather than a monolayer one enabling large-scale growth. Herein, we report substitutional fluorine doping of a chemical vapor deposition (CVD)-grown molybdenum disulfide (MoS2) monolayer film using a delicate SF6 plasma treatment. Our SF6-treated MoS2 monolayer shows a p-type doping effect with fluorine substitution. The doping concentration is controlled by the plasma treatment time (2-4.9 atom %) while maintaining the structural integrity of the MoS2 monolayer. Such reliable and tunable substitutional doping is attributed to preventing direct ion bombardment to the MoS2 monolayer by our gentle plasma treatment system. Finally, we fabricated MoS2 homojunction flexible inverter device arrays based on the pristine and SF6-treated MoS2 monolayer. A clear switching behavior is observed, and the voltage gain is approximately 8 at an applied VDD of 2 V, which is comparable to that of CVD-grown MoS2-based inverter devices reported previously. Obtained voltage gain is also stable even after 500 bending cycles at an applied strain of 0.5%.

Defect-Assisted Contact Property Enhancement in a Molybdenum Disulfide Monolayer.

Contact engineering for two-dimensional (2D) transition metal dichalcogenides (TMDCs) is crucial for realizing high-performance 2D TMDC devices, and most studies on contact properties of 2D TMDCs have mainly focused on Fermi level unpinning. Here, we investigated electrical and photoelectrical properties of chemical vapor deposition (CVD)-grown molybdenum disulfide (MoS2) monolayer devices depending on metal contacts, Ti/Pt, Ti/Au, Ti, and Ag, and particularly demonstrated the essential role of defects in MoS2 in contact properties. Remarkably, MoS2 devices with Ag contacts show a field-effect mobility of 12.2 cm2 V-1 s-1, an on/off current ratio of 7 × 107, and a photoresponsivity of 1020 A W-1, which are outstanding compared to similar devices with other metal contacts. These improvements are attributed to a reduced Schottky barrier height, thanks to the small work function of Ag and Ag-MoS2 orbital hybridization at the interface, which facilitates efficient charge transfer between MoS2 and Ag. Interestingly, X-ray photoelectron spectroscopic analysis reveals that Ag2S was formed in our defect-containing CVD-grown MoS2 monolayer, but such orbital hybridization is not observed in a nearly defect-free exfoliated MoS2. This distinction shows that defects existing in MoS2 enable Ag to effectively couple to MoS2 and correspondingly enhance multiple electrical and photoelectrical properties.

Graphene Quantum Dot Oxidation Governs Noncovalent Biopolymer Adsorption.

Graphene quantum dots (GQDs) are an allotrope of carbon with a planar surface amenable to functionalization and nanoscale dimensions that confer photoluminescence. Collectively, these properties render GQDs an advantageous platform for nanobiotechnology applications, including optical biosensing and delivery. Towards this end, noncovalent functionalization offers a route to reversibly modify and preserve the pristine GQD substrate, however, a clear paradigm has yet to be realized. Herein, we demonstrate the feasibility of noncovalent polymer adsorption to GQD surfaces, with a specific focus on single-stranded DNA (ssDNA). We study how GQD oxidation level affects the propensity for polymer adsorption by synthesizing and characterizing four types of GQD substrates ranging ~60-fold in oxidation level, then investigating noncovalent polymer association to these substrates. Adsorption of ssDNA quenches intrinsic GQD fluorescence by 31.5% for low-oxidation GQDs and enables aqueous dispersion of otherwise insoluble no-oxidation GQDs. ssDNA-GQD complexation is confirmed by atomic force microscopy, by inducing ssDNA desorption, and with molecular dynamics simulations. ssDNA is determined to adsorb strongly to no-oxidation GQDs, weakly to low-oxidation GQDs, and not at all for heavily oxidized GQDs. Finally, we reveal the generality of the adsorption platform and assess how the GQD system is tunable by modifying polymer sequence and type.

Honeycomb-Like Nitrogen-Doped Carbon 3D Nanoweb@Li2 S Cathode Material for Use in Lithium Sulfur Batteries.

Current lithium-ion batteries have a low theoretical capacity that is insufficient for use in emerging electric vehicles and energy-storage systems. The development of lithium-sulfur batteries utilizing Li2 S cathodes would be a promising option to overcome the capacity limitation. In this work, new three-dimensional (3D) honeycomb-like N-doped carbon nanowebs (HCNs) have been synthesized through a facile aqueous solution route for use as a cathode material in lithium-sulfur batteries. The Li2 S@HCNs cathode delivers a high discharge capacity of approximately 815 mAh g-1 after 65 cycles at 0.1 C, along with a superior rate capacity of approximately 568 mAh g-1 even at 2 C. The outstanding electrochemical rate performance is ascribed to their unique 3D honeycomb-like nanoweb structure, consisting of nanowires derived from polypyrrole. These properties greatly enhance the electrochemical reaction kinetics by providing efficient electron pathways and hollow channels for electrolyte transport. Nitrogen doping in the carbon nanowebs also considerably improves the chemisorption properties by tuning affinity between sulfur and oxygen functional groups on the carbon framework. The simple synthesis strategy and the resulting unique electrode structure could present a new avenue in nanostructure research for high-performance lithium-sulfur batteries.

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High-Mobility MoS2 Field-Effect Transistors.

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post-silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high-performance devices while adapting for large-area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS2 devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD-grown MoS2 film and a Ag electrode as an interfacial layer. The MoS2 field-effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field-effect mobility of 35 cm2 V-1 s-1 , an on/off current ratio of 4 × 108 , and a photoresponsivity of 2160 A W-1 , compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n-doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS2 and electrodes. This demonstration of contact interface engineering with CVD-grown MoS2 and graphene is a key step toward the practical application of atomically thin TMDC-based devices with low-resistance contacts for high-performance large-area electronics and optoelectronics.

Low-Power Complementary Logic Circuit Using Polymer-Electrolyte-Gated Graphene Switching Devices.

The modulation of the electrical properties of graphene and its device configurations for low-power consumption are important in developing graphene-based logic electronics. Here, we demonstrate the change in the charge transport in graphene from ambipolar to unipolar using surface charge transfer doping of the polymer electrolyte. Unipolar graphene field-effect transistors (GFETs) were obtained by the surface treatment of poly(acrylic acid) (PAA) for p-type and poly(ethyleneimine) (PEI) for n-type as polymer-electrolyte gates. In addition, lithium perchlorate (LiClO4) in a polymer matrix can be used for the low-gate voltage operation of GFETs (less than ±3 V) because of its high gating efficiency. Using polymer-electrolyte-gated GFETs, complementary graphene inverters were fabricated with a voltage swing of 57% and maximum voltage gain (Vgain) of 1.1 at a low supply voltage (VDD = 1 V). This is expected to facilitate the development of graphene-based logic devices with low-cost, low-power, and flexible electronics.

Novel sulfonated graphene oxide incorporated polysulfone nanocomposite membranes for enhanced-performance in ultrafiltration process.

A novel polysulfone (PSf) nanocomposite ultrafiltration (UF) membrane using sulfonated graphene oxide (SGO) as additives was fabricated and investigated. SGO nanoparticles were chemically synthesized from graphene oxide (GO) by using sulfuric acid (H2SO4) and were confirmed by Raman and Fourier transform infrared (FTIR) spectroscopy. The morphology of prepared membranes was characterized by scanning electron microscopy (SEM), energy dispersive x-ray (EDX) and atomic force microscopy (AFM). Results showed that adding small amount (less than 0.3 wt%) of SGO improved wettability, porosity and mean pore size of PSf/SGO membranes compared to the pristine PSf membrane and significantly enhanced the water flux of SGO incorporated PSf membranes. In UF performance, the nanocomposite membrane prepared by adding 1.5 w/w% SGO of PSf (designated as M1.5) showed the highest water flux result, which was 125% higher than the control PSf membrane (no SGO addition). Interestingly, there was no trade-off between water flux and bovine serum albumin (BSA) rejection, i.e more than 98% BSA rejection. The addition of SGO hydrophilic additives also showed better results in long-term BSA separation performance. The enhancement of hybrid membrane's properties was attributed to the hydrophilicity of sulfonic acid group (SO3H) on the surface of SGO additive. This study suggested that the SGO nanoparticle is a promising candidate to modify the PSf UF membranes.

Effect of ribbon width on electrical transport properties of graphene nanoribbons.

There has been growing interest in developing nanoelectronic devices based on graphene because of its superior electrical properties. In particular, patterning graphene into a nanoribbon can open a bandgap that can be tuned by changing the ribbon width, imparting semiconducting properties. In this study, we report the effect of ribbon width on electrical transport properties of graphene nanoribbons (GNRs). Monolayer graphene sheets and Si nanowires (NWs) were prepared by chemical vapor deposition and a combination of nanosphere lithography and metal-assisted electroless etching from a Si wafer, respectively. Back-gated GNR field-effect transistors were fabricated on a heavily p-doped Si substrate coated with a 300 nm-thick SiO2 layer, by O2 reactive ion etching of graphene sheets using etch masks based on Si NWs aligned on the graphene between the two electrodes by a dielectrophoresis method. This resulted in GNRs with various widths in a highly controllable manner, where the on/off current ratio was inversely proportional to ribbon width. The field-effect mobility decreased with decreasing GNR widths due to carrier scattering at the GNR edges. These results demonstrate the formation of a bandgap in GNRs due to enhanced carrier confinement in the transverse direction and edge effects when the GNR width is reduced.

Sulfur vacancy-induced reversible doping of transition metal disulfides via hydrazine treatment.

Chemical doping of transition metal dichalcogenides (TMDCs) has drawn significant interest because of its applicability to the modification of electrical and optical properties of TMDCs. This is of fundamental and technological importance for high-efficiency electronic and optoelectronic devices. Here, we present a simple and facile route to reversible and controllable modulation of the electrical and optical properties of WS2 and MoS2via hydrazine doping and sulfur annealing. Hydrazine treatment of WS2 improves the field-effect mobilities, on/off current ratios, and photoresponsivities of the devices. This is due to the surface charge transfer doping of WS2 and the sulfur vacancies formed by its reduction, which result in an n-type doping effect. The changes in the electrical and optical properties are fully recovered when the WS2 is annealed in an atmosphere of sulfur. This method for reversible modulation can be applied to other transition metal disulfides including MoS2, which may enable the fabrication of two-dimensional electronic and optoelectronic devices with tunable properties and improved performance.